JP2009227959A - Photosensitive adhesive composition, adhesion sheet, adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive adhesive composition having re-adherability after exposure, and improved in pattern formability with an alkali developer, heat resistance after re-adhesion and pasting ability at low temperature when formed into a film shape; an adhesion sheet using the composition; an adhesive pattern; a semiconductor wafer with an adhesive layer; and a semiconductor device; and a method for manufacturing the device. <P>SOLUTION: This photosensitive adhesive composition comprises (A) a polyimide having a carboxy group and/or hydroxy group; (B) a thermosetting resin; (C) a radiation-polymerizable compound; and (D) a photoinitiator, wherein the radiation-polymerizable compound containing a compound having a ≥10.0 (cal/cm<SP>3</SP>)<SP>1/2</SP>solubility parameter contains ≥20 mass% of the whole radiation-polymerizable compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive adhesive composition, an adhesive sheet, an adhesive pattern, a semiconductor wafer with an adhesive layer, a semiconductor device, and a manufacturing method thereof.

  In the manufacture of a semiconductor device such as a semiconductor package, an adhesive is conventionally used for bonding a semiconductor element and a semiconductor element mounting support member. This adhesive is required to have heat resistance and moisture resistance reliability for ensuring sufficient solder reflow resistance from the viewpoint of the reliability of the semiconductor device. In addition, in the method of bonding through a process of applying a film-like adhesive to an adherend such as a semiconductor wafer, it is applied to the adherend at a low temperature in order to reduce thermal damage to the adherend. It is desirable for the adhesive to have sufficient low temperature stickiness to allow it to be applied.

  By the way, in recent years, semiconductor packages having various forms have been proposed as electronic parts have higher performance and higher functions. Depending on the function and configuration of the semiconductor device and the method of simplifying the assembly process, an adhesive having a pattern forming ability for forming a predetermined adhesive pattern in addition to the above characteristics may be required. As an adhesive having a pattern forming ability, a photosensitive adhesive having photosensitivity is known. Photosensitivity is a function in which a portion irradiated with light is chemically changed and insolubilized or solubilized in an aqueous solution or an organic solvent. When the photosensitive adhesive having the photosensitivity is used, it is possible to form a high-definition adhesive pattern by performing exposure through a photomask and forming a pattern with a developer.

As a material constituting such a photosensitive adhesive, a polyimide resin precursor (polyamic acid) or a polyimide resin has been used so far in consideration of heat resistance (for example, see Patent Documents 1 to 3). .
JP 2000-290501 A JP 2001-329233 A Japanese Patent Laid-Open No. 11-24257

  However, with conventional photosensitive resins, it has been difficult to simultaneously achieve a high level of both pattern formation with an alkali developer and adhesion to an adherend at a low temperature. In addition, it is difficult to impart re-adhesiveness that can exhibit a sufficiently high adhesive force when thermocompression bonded after exposure.

  The present invention has been made in view of the above-described problems of the prior art, and in a photosensitive adhesive composition having re-adhesion after exposure, pattern formation by an alkali developer and heat resistance after re-adhesion The main object is to improve the low-temperature sticking property when formed into a film.

The photosensitive adhesive composition according to the present invention includes (A) a polyimide having a carboxyl group and / or a hydroxyl group, (B) a thermosetting resin, (C) a radiation polymerizable compound, and (D) a photoinitiator. Containing. The radiation-polymerizable compound contains a compound having a solubility parameter (hereinafter referred to as “SP value” in some cases) of 10.0 (cal / cm ³ ) ^1/2 or more in an amount of 20% by mass or more of the whole radiation-polymerizable compound. .

  The photosensitive adhesive composition according to the present invention has re-adhesiveness after pattern formation by having the above-mentioned specific structure, and has a film-formability and heat resistance after re-adhesion with an alkaline developer. It is sufficiently excellent in terms of low temperature sticking property when formed into a shape.

10.0 (cal / cm ³ ) The above compound having an SP value of ^1/2 or more (hereinafter sometimes referred to as “high SP value compound”) is formed from an amide group, a urethane group, an isocyanuric group, an imide group, and a hydroxyl group. It preferably has at least one group selected from the group consisting of

  The high SP value compound is preferably a bifunctional to tetrafunctional acrylate and / or methacrylate. More specifically, the high SP value compound is preferably a compound represented by the following general formula (1) or (2).

In formula (1), R ¹ represents a divalent organic group having 2 to 30 carbon atoms, and R ² and R ³ each independently represents an organic group having a methacrylate group or an acrylate group. In formula (2), R ⁴ and R ⁵ represent an organic group having a methacrylate group or an acrylate group, and R ⁶ represents an organic group having a hydroxyl group, a methacrylate group or an acrylate group.

  The molecular weight of the high SP value compound is preferably 2000 or less. Thereby, it is possible to impart finer pattern formability and better adhesion after exposure and development. Further, when assembling a semiconductor device or an electronic component, stable adhesiveness and sufficient heat resistance can be expressed, and a highly reliable semiconductor device or electronic component can be obtained.

  The thermosetting resin is preferably an epoxy resin from the viewpoint of handleability and compatibility with polyimide. By using an epoxy resin, the storage stability, high-temperature adhesiveness and heat resistance of the photosensitive adhesive composition can be further improved.

  The polyimide preferably has a glass transition temperature (Tg) of 150 ° C. or lower and a weight average molecular weight of 5,000 to 150,000. Thereby, the storage stability, high temperature adhesiveness, and heat resistance of the photosensitive adhesive composition can be further improved.

  The polyimide is preferably alkali-soluble. Thereby, a finer pattern can be formed by exposure and development, and further, the photosensitive adhesive composition can be bonded to an adherend such as a semiconductor wafer or glass at a lower temperature.

  The polyimide is preferably obtained by reacting tetracarboxylic dianhydride and diamine. Such polyimide can easily achieve a Tg of 150 ° C. or lower, and is particularly excellent in alkali solubility, solvent solubility, and compatibility with other compounding components.

  The diamine may contain an aromatic diamine represented by the following chemical formula (3) or (4).

The diamine may contain 10 to 90 mol% of an aliphatic ether diamine represented by the following general formula (5) based on the total diamine. In formula (5), Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and n ¹ represents an integer of ¹ to 80.

The said diamine may contain 1-20 mol% of siloxane diamine represented by following General formula (6) with respect to the whole diamine. In formula (6), R ⁷ and R ⁸ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each Independently, it represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and n ² represents an integer of 1 to 5.

  The said tetracarboxylic dianhydride may contain 40 mol% or more of the compound represented by following Chemical formula (7) with respect to the whole tetracarboxylic dianhydride.

  In another aspect, the present invention relates to an adhesive sheet comprising a film-like adhesive layer made of the photosensitive adhesive composition according to the present invention. The adhesive sheet may further include a base material, and an adhesive layer may be provided on one surface of the base material. The adhesive sheet may further include a dicing sheet, and the dicing sheet and the adhesive layer may be laminated.

  These adhesive sheets are preferably used for manufacturing a highly reliable semiconductor device while suppressing thermal damage to the adherend when manufacturing a semiconductor device or the like after re-adhesion after exposure. Can do.

  In still another aspect, the present invention is formed by exposing a film-like adhesive layer comprising the photosensitive adhesive composition according to the present invention, and developing the exposed adhesive layer using an alkaline developer. To the adhesive pattern. Such an adhesive pattern has sufficient heat resistance after re-adhesion.

  In still another aspect, the present invention relates to a semiconductor wafer with an adhesive layer, comprising: a semiconductor wafer; and an adhesive layer made of the photosensitive adhesive composition according to the present invention provided on one surface of the semiconductor wafer. .

  In still another aspect, the present invention relates to a semiconductor device including a support member, a semiconductor element mounted on the support member, and an adhesive layer interposed between the support member and the semiconductor element. The adhesive layer is formed by the photosensitive adhesive composition according to the present invention.

  Moreover, this invention is the process of forming an adhesive pattern by exposing the adhesive bond layer which consists of the photosensitive adhesive composition which concerns on the said invention, and developing the adhesive bond layer after exposure using an alkali developing solution. And a method of manufacturing a semiconductor device comprising a step of bonding a semiconductor element and a support member on which the semiconductor element is mounted via an adhesive pattern.

  According to the above method, a semiconductor device having high reliability can be obtained while suppressing thermal damage to the adherend.

  According to the present invention, the photosensitivity having a high re-adhesion property after exposure is sufficiently excellent in terms of the pattern formability by an alkali developer and the heat resistance after re-adhesion, and the low temperature stickability when formed into a film. An adhesive composition is obtained. Further, the photosensitive adhesive composition of the present invention has a high dissolution rate in an alkali developer. The film-like adhesive layer (adhesive film) comprising the photosensitive adhesive composition of the present invention can be attached to an adherend at a relatively low temperature, and thermal damage to peripheral materials is suppressed. Therefore, a highly reliable semiconductor device and electronic component can be obtained.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  1, 2 and 3 are schematic cross-sectional views each showing an embodiment of an adhesive sheet. The adhesive sheet 100 shown in FIG. 1 is comprised from the adhesive bond layer 1 which is the photosensitive adhesive composition shape | molded by the film form. The adhesive sheet 110 shown in FIG. 2 is comprised from the base material 3 and the adhesive bond layer 1 provided on one surface of this. The adhesive sheet 120 shown in FIG. 3 includes a base material 3, an adhesive layer 1 provided on one surface of the base material 3, and a cover film 2. The photosensitive adhesive composition for forming the adhesive layer 1 includes (A) a polyimide having a carboxyl group and / or a hydroxyl group, (B) a thermosetting resin, (C) a radiation polymerizable compound, and (D). Containing a photoinitiator. Details of the photosensitive adhesive composition will be described later.

  The adhesive sheet 100 of FIG. 1 mixes the photosensitive adhesive composition which concerns on below-mentioned embodiment in an organic solvent, knead | mixes a liquid mixture, prepares a varnish, and forms the layer of this varnish on the base material 3 The base material 3 can be obtained by drying the varnish layer by heating. The adhesive layer 1 can be stored and used in the state of the adhesive sheet 110 or 120 without removing the base material 3.

  The above mixing and kneading can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. In addition, it dries on the conditions which (B) thermosetting resin does not fully react during drying, and the solvent fully volatilizes. Specifically, the varnish layer is dried by heating at 60 to 180 ° C. for 0.1 to 90 minutes. The preferred thickness of the varnish layer before drying is 1 to 100 μm. If this thickness is less than 1 μm, the adhesive fixing function tends to be impaired, and if it exceeds 100 μm, the residual volatile matter described later tends to increase.

  The preferred residual volatile content of the adhesive layer 1 is 10% by mass or less. If this residual volatile content exceeds 10% by mass, voids tend to remain inside the adhesive layer due to foaming due to solvent volatilization during assembly heating, and the moisture resistance reliability tends to be impaired. There is a tendency that the possibility of contamination of surrounding materials or members due to the generated volatile components is increased. In addition, the measurement conditions of said residual volatile component are as follows. That is, the initial mass of the adhesive layer cut to a size of 50 mm × 50 mm is M1, the mass after being heated in an oven at 160 ° C. for 3 hours is M2, and {(M1-M2) / M1} × 100 = remaining It is a value calculated by volatile content (%).

  Specifically, the temperature at which the thermosetting resin does not sufficiently react is determined by using DSC (for example, “DSC-7 type” (trade name) manufactured by PerkinElmer Co., Ltd.) The temperature is equal to or lower than the peak temperature of the heat of reaction when measured under the conditions of temperature rate: 5 ° C./min and measurement atmosphere: air.

  The organic solvent used for preparing the varnish, that is, the varnish solvent is not particularly limited as long as the material can be uniformly dissolved or dispersed. Examples include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidinone.

  The substrate 3 is not particularly limited as long as it can withstand the above drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, or a methylpentene film can be used as the substrate 3. The film as the substrate 3 may be a multilayer film in which two or more kinds are combined, or the surface may be treated with a release agent such as silicone or silica.

  An adhesive layer and a dicing sheet can also be laminated. The dicing sheet is a sheet in which a pressure-sensitive adhesive layer is provided on a substrate, and the pressure-sensitive adhesive layer may be either a pressure-sensitive type or a radiation curable type. The base material is preferably a base material that can be expanded. By using such an adhesive sheet, a dicing / die bonding integrated adhesive sheet having both a function as a die bond film and a function as a dicing sheet can be obtained.

  Specific examples of the dicing / die bonding integrated adhesive sheet include an adhesive sheet 130 in which a base material 7, an adhesive layer 6 and an adhesive layer 1 are formed in this order, as shown in FIG.

  FIG. 5 is a top view showing an embodiment of a semiconductor wafer with an adhesive layer, and FIG. 6 is an end view taken along line VI-VI in FIG. A semiconductor wafer 20 with an adhesive layer shown in FIGS. 5 and 6 includes a semiconductor wafer 8 and an adhesive layer 1 similar to the adhesive sheet provided on one surface of the semiconductor wafer 8.

  The semiconductor wafer 20 with an adhesive layer is obtained by laminating the adhesive layer 1 on the semiconductor wafer 8 while heating. Since the adhesive layer 1 is a sheet made of a photosensitive adhesive composition, which will be described later, it can be attached to the semiconductor wafer 8 at a low temperature of about room temperature (25 ° C.) to 150 ° C., for example.

  7 and 9 are top views showing an embodiment of the adhesive layer pattern. 8 is an end view taken along line VIII-VIII in FIG. 7, and FIG. 10 is an end view taken along line XX in FIG. The adhesive patterns 1a and 1b shown in FIGS. 7, 8, 9, and 10 are formed on a semiconductor wafer 8 as an adherend so as to have a pattern along a substantially square side or a square pattern.

  The adhesive patterns 1a and 1b are obtained by forming an adhesive layer 1 made of a photosensitive adhesive composition on a semiconductor wafer 8 as an adherend to obtain a semiconductor wafer 20 with an adhesive layer. It is formed by exposing through a mask and developing the exposed adhesive layer 1 with an alkaline developer. Thereby, semiconductor wafers 20a and 20b with an adhesive layer in which adhesive patterns 1a and 1b are formed are obtained.

  Embodiments of a semiconductor device will be specifically described with reference to the drawings. In recent years, semiconductor devices having various structures have been proposed, and the use of the photosensitive adhesive composition of the present invention is not limited to the semiconductor devices having the structures described below.

  FIG. 11 is a schematic cross-sectional view showing an embodiment of a semiconductor device. In the semiconductor device 200 shown in FIG. 11, the semiconductor element 12 is bonded to the semiconductor element mounting support member 13 via the adhesive layer 1, and the connection terminal of the semiconductor element 12 is electrically connected to the external connection terminal via the wire 14. It is connected. The semiconductor element 12 is sealed with a sealing material 15.

  FIG. 12 is a schematic cross-sectional view showing another embodiment of the semiconductor device. In the semiconductor device 210 shown in FIG. 12, the first-stage semiconductor element 12a is bonded via the adhesive layer 1 to the semiconductor-element mounting support member 13 on which the terminals 16 are formed, and on the first-stage semiconductor element 12a. Further, the second-stage semiconductor element 12 b is bonded via the adhesive layer 1. The connection terminals of the first-stage semiconductor element 12 a and the second-stage semiconductor element 12 b are electrically connected to the external connection terminals via the wires 14. The semiconductor elements 12 a and 12 b are sealed with a sealing material 15. Thus, the photosensitive adhesive composition of the present embodiment can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

  In the semiconductor device (semiconductor package) shown in FIGS. 11 and 12, for example, the semiconductor wafer 20b with an adhesive layer shown in FIG. 9 is diced along the broken line D, and the semiconductor element with the adhesive layer after dicing is mounted on the semiconductor element. It can be obtained by thermocompression bonding to the supporting member 13 and bonding them together, followed by steps such as a wire bonding step and, if necessary, a sealing step with a sealing material. The heating temperature in the thermocompression bonding is usually 20 to 250 ° C., the load is usually 0.01 to 20 kgf, and the heating time is usually 0.1 to 300 seconds.

  The photosensitive adhesive composition for forming the adhesive layer 1 in the above embodiment includes (A) a polyimide having a carboxyl group and / or a hydroxyl group, (B) a thermosetting resin, and (C) a radiation polymerizable compound. And (D) a photoinitiator. A radiation polymerizable compound contains 20 mass% or more of high SP value compounds.

By providing the above-described configuration, the photosensitive adhesive composition according to the present embodiment has a pattern forming property by an alkali developer and heat resistance after re-adhesion, and a low temperature sticking property when formed into a film shape. Excellent enough. The pattern forming property means that a photosensitive adhesive composition in the form of a film is laminated on an adherend such as a silicon wafer by pressing at a temperature of preferably 20 to 150 ° C. After placing a mask and using a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd.), exposure to ultraviolet rays under the conditions of exposure dose: 100 to 1000 mJ / cm ² , tetramethylammonium hydride (TMAH) 1.0 to 5.0 It means the performance by which a good pattern is formed when spray development is performed using an aqueous solution containing 1% by mass or 1 to 10% by mass of sodium carbonate, preferably 2.38% by mass of TMAH. The line width after pattern formation is preferably in the range of 0.01 mm to 20 mm.

When the SP value of the above high SP value compound is less than 10.0 (cal / cm ³ ) ^1/2 or when the high SP value is less than 20% by mass of the total radiation polymerizable compound Moreover, the adhesiveness of a photosensitive adhesive composition and the fall of pattern formation may be caused. When the SP value is smaller than 10.0 (cal / cm ³ ) ^1/2 , the resulting photosensitive adhesive composition proceeds in the direction of lower polarity or hydrophobicity. It is presumed that the formability is lowered, and that the surface energy is lowered, leading to a decrease in adhesiveness. The SP value is calculated by the following formula.

(Equation 1)
SP value (δ) = ΣΔF / ΣΔυ

  The above ΣΔF is the sum of the molar attractive constants of various atoms or various atomic groups at 25 ° C., ΣΔυ is the sum of the molar volumes of various atoms or various atomic groups, and the values of ΔF and Δυ of various atoms or various atomic groups are: Okitsu's constant (Toshinao Okitsu, “Adhesion”, Vol. 40, No. 8, p342 (1996)) was used.

  In the case where the adhesive sheet of the present invention is attached to the back surface of the wafer, the application temperature is preferably 20 to 200 ° C., more preferably 20 to 150 ° C. from the viewpoint of suppressing warpage of the semiconductor wafer, It is especially preferable that it is 25-100 degreeC. In order to enable attachment at the above temperature, it is preferable to set the Tg of the adhesive layer to 150 ° C. or less. Therefore, the glass transition temperature (Tg) of the polyimide having (A) carboxyl group and / or hydroxyl group used in the photosensitive adhesive composition is preferably 150 ° C. or lower, more preferably −20 to 100 ° C. Preferably, it is -20-80 degreeC. (A) If the Tg of the polyimide having a carboxyl group and / or a hydroxyl group exceeds 150 ° C, the bonding temperature to the wafer back surface is likely to exceed 200 ° C, and warping occurs after bonding to the wafer back surface. If the Tg is less than −20 ° C., the tackiness of the film surface in the B-stage state becomes too strong, and the handleability tends to deteriorate. Here, the B stage means a state in which the resin composition is semi-cured, and the tackiness means the stickiness. When determining the composition of the polyimide resin described later, it is preferable to design the Tg to be 150 ° C. or lower.

  (A) It is preferable that the weight average molecular weight of the polyimide which has a carboxyl group and / or a hydroxyl group is 5000-150,000, It is more preferable that it is 10,000-100000, It is still more preferable that it is 10,000-80000. When the weight average molecular weight is within the above range, the strength, flexibility, and tackiness when the photosensitive adhesive composition is made into a sheet or film are good, and the heat fluidity is good. Therefore, it is possible to ensure good embedding property to the wiring step on the substrate surface. When the weight average molecular weight is less than 5,000, the film formability and heat resistance tend to be deteriorated. When the weight average molecular weight is more than 150,000, the fluidity during heat is deteriorated and the embedding property to the unevenness on the substrate is lowered. There is also a tendency, and (A) the solubility of the polyimide having a carboxyl group and / or a hydroxyl group in an alkaline developer tends to decrease.

  (A) By making Tg and weight average molecular weight of the polyimide which has a carboxyl group and / or a hydroxyl group in the said range, while being able to hold down the bonding temperature to a wafer back surface low, a semiconductor element is for semiconductor element mounting The heating temperature (die bonding temperature) for bonding and fixing to the support member can also be lowered, and an increase in warpage of the semiconductor element can be suppressed. Moreover, the fluidity | liquidity at the time of die bonding and the developability which are the characteristics of this invention can be provided effectively.

  Said Tg is the main dispersion peak temperature when (A) the polyimide which has a carboxyl group and / or a hydroxyl group is formed into a film. Using a rheometer viscoelasticity analyzer “RSA-2” (trade name), the temperature was increased at a rate of 5 ° C./minute, the frequency was 1 Hz, the measurement temperature was −150 to 300 ° C., and the tan δ peak near Tg. The temperature was measured and used as the main dispersion temperature. Said weight average molecular weight is a weight average molecular weight when measured by polystyrene conversion using Shimadzu Corporation high performance liquid chromatography “C-R4A” (trade name).

  (A) A polyimide having a carboxyl group and / or a hydroxyl group can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in the organic solvent, tetracarboxylic dianhydride and diamine are equimolar, or if necessary, the total amount of diamine is preferably 0.00 with respect to the total 1.0 mol of tetracarboxylic dianhydride. The composition ratio is adjusted in the range of 5 to 2.0 mol, more preferably 0.8 to 1.0 mol (the order of addition of each component is arbitrary), and the addition reaction is performed at a reaction temperature of 80 ° C. or lower, preferably 0 to 60 ° C. . As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide resin precursor, is generated. In addition, in order to suppress the fall of the various characteristics of an adhesive composition, it is preferable that said tetracarboxylic dianhydride is what recrystallized and refined with acetic anhydride.

  In addition, about the composition ratio of the tetracarboxylic dianhydride and diamine in the said condensation reaction, when the total of diamine exceeds 2.0 mol with respect to the total 1.0 mol of tetracarboxylic dianhydride, the polyimide obtained There exists a tendency for the quantity of the amine terminal polyimide oligomer to increase in resin, and when the weight average molecular weight of a polyimide resin becomes small, there exists a tendency for the various characteristics including the heat resistance of adhesive composition to fall. On the other hand, if the total amount of diamines is less than 0.5 mol, the amount of acid-terminated polyimide oligomer tends to increase, the weight average molecular weight of the polyimide resin decreases, and various properties including the heat resistance of the adhesive composition Tends to decrease.

  It is preferable to appropriately determine the composition ratio of the tetracarboxylic dianhydride and the diamine so that the resulting polyimide resin has a weight average molecular weight of 5000 to 150,000.

  The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed, a chemical ring closure method using a dehydrating agent, or the like.

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2 , 3,4-Butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2 , 2]-Oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3 4-dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) ) Phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid) Anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuran) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following general formula (8) An acid dianhydride etc. are mentioned.

［式中、ａは２〜２０の整数を示す。］

[Wherein, a represents an integer of 2 to 20. ]

  The tetracarboxylic dianhydride represented by the general formula (8) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol. Specifically, 1,2- (ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5 -(Pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) Bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (tri Riteto anhydride) and the like.

  The tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride represented by the following formula (9) or (10) from the viewpoint of imparting good solubility in a solvent and moisture resistance reliability.

  The above tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  The diamine used as a raw material for the polyimide resin preferably includes an aromatic diamine represented by the following formula (11), (12), (13) or (14). These diamines represented by the following formulas (11) to (14) are preferably 1 to 50 mol% of the total diamines.

  There is no restriction | limiting in particular as other diamine used as a raw material of the said polyimide resin, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'- diaminodiphenyl ether, 3,4'-diaminodiphenyl ether 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethermethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diamino Diphenyls Phon, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3 '-Diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2'-(3,4'-diaminodiphenyl ) Propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2, 2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) Xyl) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4 -(3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane Bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3 -Aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, aromatic diamines such as 3,5-diaminobenzoic acid, 3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (15), aliphatic represented by the following general formula (16) Examples thereof include diamines and siloxane diamines represented by the following general formula (6).

［式中、Ｑ^１、Ｑ^２及びＱ^３は各々独立に、炭素数１〜１０のアルキレン基を示し、ｂは２〜８０の整数を示す。］

[Wherein, Q ¹ , Q ² and Q ³ each independently represents an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 2 to 80. ]

［式中、ｃは５〜２０の整数を示す。］

[Wherein c represents an integer of 5 to 20. ]

［式中、Ｒ^７及びＲ^８は各々独立に、炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｒ^９、Ｒ^１０、Ｒ^１１及びＲ^１２は各々独立に、炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｎ^２は１〜５の整数を示す。］

[Wherein R ⁷ and R ⁸ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and n ² represents an integer of 1 to 5. ]

  Specifically as aliphatic ether diamine represented by the said General formula (15), following formula;

で表される脂肪族ジアミンの他、下記式（１７）で表される脂肪族エーテルジアミンが挙げられる。

In addition to the aliphatic diamine represented by the formula, an aliphatic ether diamine represented by the following formula (17) is exemplified.

［式中、ｅは０〜８０の整数を示す。］

[In formula, e shows the integer of 0-80. ]

  Specific examples of the aliphatic diamine represented by the general formula (16) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6. -Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diamino And cyclohexane.

Specific examples siloxane diamine represented by general formula (6), as ^{n 2} in the formula (6) is 1, 1,1,3,3-tetramethyl-1,3-bis (4 -Aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2 -Aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2 -Aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3 -Aminobutyl) disiloxane, 1,3-dimethyl-1,3 -Dimethoxy-1,3-bis (4-aminobutyl) disiloxane and the like, and n ² is 2, and 1,1,3,3,5,5-hexamethyl-1,5-bis (4 -Aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3 , 3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1, 5-bis (4-aminobutyl) to Lisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5, Examples include 5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.

  The diamine mentioned above can be used individually by 1 type or in combination of 2 or more types.

  The said polyimide resin can be used individually by 1 type or in mixture (blend) of 2 or more types as needed.

  As described above, when determining the composition of the polyimide resin, it is preferable to design the Tg to be 150 ° C. or lower. The diamine that is a raw material of the polyimide resin is represented by the general formula (17). It is preferable to use an aliphatic ether diamine. Specific examples of the aliphatic ether diamine represented by the general formula (17) include Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED- manufactured by Sun Techno Chemical Co., Ltd. And aliphatic diamines such as polyoxyalkylene diamines such as 900, ED-2000, EDR-148, BASF (manufactured) polyetheramine D-230, D-400, and D-2000. These diamines are preferably 1 to 80 mol%, more preferably 5 to 60 mol% of the total diamine. If this amount is less than 1 mol%, it tends to be difficult to impart low-temperature adhesiveness and fluidity during heat. On the other hand, if it exceeds 80 mol%, the Tg of the polyimide resin becomes too low, Self-supporting tends to be impaired.

  The polyimide resin can be obtained by a reaction between a tetracarboxylic dianhydride and a diamine having a carboxyl group and an amino group, whereby a carboxyl group derived from the diamine is introduced into the polyimide. (A) The polyimide having a carboxyl group and / or a hydroxyl group is particularly preferably a resin having a Tg of 150 ° C. or less and an Mw of 5000 to 150,000 by appropriately adjusting the type of diamine, its charging ratio, reaction conditions, and the like.

  In the photosensitive adhesive composition, (A) the content of the polyimide having a carboxyl group and / or a hydroxyl group is 5 to 5 on the basis of the total solid content of the photosensitive adhesive composition from the viewpoint of pattern formability and adhesiveness. It is preferably 90% by mass, and more preferably 20 to 80% by mass. When this content is less than 20% by mass, the pattern formability tends to be impaired, and when it exceeds 80% by mass, the pattern formability and adhesiveness tend to decrease.

  (B) The thermosetting resin refers to a reactive compound capable of causing a crosslinking reaction by heat. Examples of such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, From xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, cyclopentadiene Examples thereof include a thermosetting resin synthesized and a thermosetting resin by trimerization of aromatic dicyanamide. Among these, an epoxy resin, a cyanate resin, and a bismaleimide resin are preferable in that an excellent adhesive force can be given at a high temperature, and an epoxy resin is particularly preferable from the viewpoint of handleability and compatibility with polyimide. These thermosetting resins can be used alone or in combination of two or more.

  (B) As a thermosetting resin, what contains at least 2 or more epoxy group in a molecule | numerator is preferable, and the glycidyl ether type epoxy resin of a phenol is more preferable from the point of sclerosis | hardenability or hardened | cured material characteristic. Examples of such resins include bisphenol A type (or AD type, S type, and F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct. Bisphenol A glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolak resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclo Examples include glycidyl ether of pentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. It is. These can be used alone or in combination of two or more.

  (B) As the thermosetting resin, use a high-purity product in which impurity ions such as alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less. However, it is preferable from the viewpoint of preventing electromigration and preventing corrosion of metal conductor circuits.

  In the photosensitive adhesive composition, the content of the (B) thermosetting resin is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the polyimide (A) having a carboxyl group and / or a hydroxyl group. 2 to 50 parts by mass is more preferable. When this content exceeds 200 mass parts, the solubility to alkaline aqueous solution will fall, and there exists a tendency for pattern formation to fall. On the other hand, when the content is less than 2 parts by mass, the high-temperature adhesiveness tends to decrease.

  When an epoxy resin is selected as the thermosetting resin, an epoxy resin curing agent can be included in the photosensitive adhesive composition as necessary. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acids. Examples include dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines. Among these, phenol compounds are preferable, and phenol compounds having at least two phenolic hydroxyl groups in the molecule are more preferable. Examples of such compounds include phenol novolak, cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol novolak, dicyclopentadiene phenol novolak, xylylene-modified phenol novolak, naphthol compound, trisphenol compound, tetrakisphenol novolak, bisphenol. A novolak, poly-p-vinylphenol, phenol aralkyl resin and the like. Among these, those having a number average molecular weight in the range of 400 to 1500 are preferable. Thereby, the outgas at the time of heating which causes the contamination of the semiconductor element or the device at the time of assembling the semiconductor device can be suppressed.

  Furthermore, the photosensitive adhesive composition can contain a curing accelerator as required. The curing accelerator is not particularly limited as long as it cures an epoxy resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4- Examples thereof include methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate. As for content of the hardening accelerator in a photosensitive adhesive composition, 0.01-50 mass parts is preferable with respect to 100 mass parts of epoxy resins.

  (C) The high SP value compound contained in the radiation adhesive composition preferably has at least one group selected from the group consisting of an amide group, a urethane group, an isocyanuric group, an imide group and a hydroxyl group. Moreover, it is preferable that a high SP value compound is a 2-4 functional acrylate and / or methacrylate.

The high SP value compound contained in the photosensitive adhesive composition is preferably N-acryloyloxyethyl hexahydrophthalimide, isocyanuric acid modified diacrylate, isocyanuric acid modified dimethacrylate, isocyanuric acid modified triacrylate, isocyanuric acid modified trimethacrylate. , Ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, ε-caprolactone-modified tris (methacryloxyethyl) isocyanurate, urethane acrylate, urethane methacrylate, epoxy acrylate, epoxy methacrylate, polyfunctional (meth) acrylate having an imide skeleton, It is selected from polyfunctional (meth) acrylate having a hydroxyl group, urea methacrylate and a compound represented by the following general formula (18). Among these, those having an SP value of 10.0 (cal / cm ³ ) ^1/2 or more are selected.

［式中、Ｒ^４１及びＲ^４２は各々独立に、水素原子又はメチル基を示し、ｆ及びｇは各々独立に、１〜２０の整数を示す。］

[Wherein, R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a methyl group, and f and g each independently represents an integer of 1 to 20. ]

  Among these, urethane acrylate or urethane methacrylate represented by the above general formula (1), and isocyanuric acid modified diacrylate, isocyanuric acid modified dimethacrylate, isocyanuric acid modified trimethyl represented by the above general formula (2). Acrylate or isocyanuric acid modified trimethacrylate is preferred.

  The urethane acrylate or urethane methacrylate of the formula (1) is produced, for example, by a reaction of a diol, an isocyanate compound represented by the following general formula (19), and a compound represented by the following general formula (20).

［式中、Ｒ^４３は炭素数１〜３０の２価又は３価の有機基を示し、ｈは０又は１を示す。］

[Wherein, R ⁴³ represents a divalent or trivalent organic group having 1 to 30 carbon atoms, and h represents 0 or 1. ]

［式中、Ｒ^４４は水素原子又はメチル基を示し、Ｒ^４５はエチレン基又はプロピレン基を示す。］

[Wherein, R ⁴⁴ represents a hydrogen atom or a methyl group, and R ⁴⁵ represents an ethylene group or a propylene group. ]

  The urea methacrylate is produced, for example, by a reaction between a diamine represented by the following general formula (21) and a compound represented by the following general formula (22).

［式中、Ｒ^４６は炭素数２〜３０の２価の有機基を示す。］

[Wherein, R ⁴⁶ represents a divalent organic group having 2 to 30 carbon atoms. ]

［式中、ｉは０又は１を示す。］

[Wherein i represents 0 or 1; ]

  In addition to the above compounds, a compound having at least one ethylenically unsaturated group and a functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, and a carboxyl group is added to a vinyl copolymer containing a functional group. A radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain obtained by the reaction can be used.

  In the photosensitive adhesive composition of the present invention, the content of the radiation polymerizable compound containing 20% by mass or more of the (C) high SP value compound in the whole radiation polymerizable compound is 10 with respect to 100 parts by mass of the component (A). It is preferable that it is -200 mass parts, and it is more preferable that it is 20-100 mass parts. When this content exceeds 200 parts by mass, the fluidity at the time of thermal melting is lowered due to polymerization, the adhesiveness at the time of thermocompression bonding is lowered, and the tack tends to be increased and the handleability tends to be lowered. On the other hand, if it is less than 10 parts by mass, the solvent resistance after photocuring by exposure tends to be low, and it tends to be difficult to form a pattern.

  The (C) radiation-polymerizable compound preferably has a 5% mass reduction temperature of 150 ° C. or higher, more preferably 180 ° C. or higher, and 200 ° C. or higher from the viewpoints of adhesiveness and heat resistance. Is more preferred, and most preferred is 260 ° C. or higher. Here, the 5% mass reduction temperature means that the sample is heated at a rate of 10 ° C./min with a flow rate of 10 ° C./min using a differential thermothermal gravimetric simultaneous measurement apparatus (trade name “TG / DTA6300” manufactured by SII Nanotechnology). It means 5% mass loss temperature when measured under (400 ml / min).

(C) The radiation polymerizable compound may include a compound having an SP value of less than 10.0 (cal / cm ³ ) ^1/2 . Although it does not specifically limit as a compound whose SP value is less than 10.0 (cal / cm < ³ >) < ^1/2 >, For example, polyether acrylate, polyether methacrylate, polyester acrylate, polyester methacrylate, acrylic acrylate, bisphenol A-EO Modified diacrylate, bisphenol F-EO modified diacrylate, long chain diol modified diacrylate (4 to 10 carbon atoms), ethylene glycol modified diacrylate, dimethylol-tricyclodecane diacrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate Examples thereof include glycidyl ether, glycidyl methacrylate, and siloxane-modified diacrylate. These may contain multiple types.

In the photosensitive adhesive composition, the ratio of the high SP value compound to the whole radiation compound is more preferably 30% by mass or more. At this time, from the viewpoint of adhesiveness, it is preferable that the average value of the SP values of the entire radiation polymerizable compound is 10.0 (cal / cm ³ ) ^1/2 or more.

When the ratio of the high SP value compound is 50% by mass or less, the radiation polymerizable compound having an SP value of less than 10.0 (cal / cm ³ ) ^1/2 used in combination with the high SP value compound is not particularly limited. However, it is preferable to use those having a hydrophilic group such as propylene glycol and ethylene glycol. Thereby, even when a radiation polymerizable compound having an SP value of less than 10.0 (cal / cm ³ ) ^1/2 is used in combination, a good pattern forming property can be obtained.

The SP value of the compound having a SP value of less than 10.0 (cal / cm ³ ) ^½ preferably has a 5% mass reduction temperature of 150 ° C. or higher and 180 ° C. or higher from the viewpoint of heat resistance reliability. Is more preferably 200 ° C. or higher, and most preferably 260 ° C. or higher.

  Here, it becomes possible to reduce stress and warp by using a radiation polymerizable compound having a high functional group equivalent. The radiation-polymerizable compound having a high functional group equivalent preferably has a polymerization functional group equivalent of 200 eq / g or more, more preferably 300 eq / g or more, and most preferably 400 eq / g or more. In the photosensitive adhesive composition, when developability and adhesiveness are good, and low stress and low warpage are required, a glycol skeleton having a polymerizable functional group equivalent of 200 eq / g or more as a radiation polymerizable compound and / or A radiation polymerizable compound having a urethane group and / or an isocyanuric group may be used.

  The photosensitive adhesive composition further contains (D) a photoinitiator. Examples of the (D) photoinitiator include a photoradical initiator that generates a free radical by irradiation, a photobase generator that generates a base by irradiation, a photoacid generator that generates an acid by irradiation, and the like. . (D) As a photoinitiator, in order to improve a sensitivity, what has an absorption band in 300-500 nm is preferable, and it is more preferable that the molecular extinction coefficient with respect to the light of wavelength 365nm is 1000 ml / g * cm or more. Moreover, it is preferable to use the (D) photoinitiator whose 5% mass reduction | decrease temperature is 150 degreeC or more at the point of an outgas reduction and high temperature adhesive improvement. As for the molecular extinction coefficient, a 0.001% by mass acetonitrile solution of the sample is prepared, and the absorbance of this solution is measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, “U-3310” (trade name)). Is required.

(D) Specific examples of the photoinitiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4- Methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Aromatic ketones such as hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone , Benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ether, benzoin such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5 -Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) 2,4,5-triarylimidazole dimer such as -4,5-diphenylimidazole dimer, 9-phenyl Acridine derivatives such as acridine, 1,7-bis (9,9′-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,4) Bisacylphosphine oxides such as 6, -trimethylbenzoyl) -phenylphosphine oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- ( O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like. These can be used individually by 1 type or in combination of 2 or more types.
In addition, when the thickness of the photosensitive adhesive resin composition is 30 μm or more, it is preferable to use a photoinitiator that performs photobleaching.

  In the photosensitive adhesive resin composition, a photobase generator may be added as (D) a photoinitiator. The photobase generator is not particularly limited as long as it is a compound that generates a base upon irradiation with radiation. As the base to be generated, a strongly basic compound is preferable in terms of reactivity and curing speed. In general, a pKa value that is a logarithm of an acid dissociation constant is used as a basic index, and a base having a pKa value in an aqueous solution of 7 or more is preferable, and a base of 9 or more is more preferable.

  Examples of such basic compounds include imidazole derivatives such as imidazole, 2,4-dimethylimidazole and 1-methylimidazole, piperazine derivatives such as piperazine and 2,5-dimethylpiperazine, piperidine, 1,2- Piperidine derivatives such as dimethylpiperidine, proline derivatives, trialkylamine derivatives such as trimethylamine, triethylamine, and triethanolamine, pyridine with an amino group or alkylamino group substituted at the 4-position of 4-methylaminopyridine, 4-dimethylaminopyridine, etc. Derivatives, pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine, alicyclic amine derivatives such as triethylenediamine and 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzylmethylamine, benzyldimethyl Triethanolamine, and the like benzylamine derivatives such as benzyl diethylamine.

  Examples of the photobase generator that generates the basic compound by irradiation with radiation include, for example, Journal of Photopolymer Science and Technology 12, 313-314 (1999), Chemistry of Materials 11, 170-176 (1999). ) And the like can be used. Since these produce highly basic trialkylamines by irradiation with actinic rays, they are optimal for curing epoxy resins.

  As the photobase generator, the carbamic acid derivatives described in Journal of American Chemical Society 118, 12925 (1996), Polymer Journal 28, 795 (1996), and the like can be used.

  An oxime derivative that generates a primary amino group upon irradiation with actinic rays, and a commercially available 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba) as a photo radical generator Irgacure 907 from Specialty Chemicals, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 from Ciba Specialty Chemicals), hexaarylbisimidazole derivative (halogen, Substituents such as alkoxy groups, nitro groups, and cyano groups may be substituted with phenyl groups), benzoisoxazolone derivatives, and the like.

  In addition to the above-mentioned base generators based on actinic rays, basic compounds are also generated by photo-Fries rearrangement, photo-Claisen rearrangement (photo-Cleisen rearrangement), Curtius rearrangement (Curtius rearrangement), and Stevens rearrangement (Stevens rearrangement), thereby curing the epoxy resin It can be performed.

  The base generator may be used as a low molecular compound having a molecular weight of 500 or less, or a compound having a base generating group introduced into the main chain and / or side chain of a polymer. The molecular weight in this case is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 30,000 from the viewpoints of adhesiveness and fluidity.

  Since these compounds do not show reactivity with the epoxy resin in a state where they are not irradiated with radiation at room temperature (25 ° C.), they are characterized by excellent storage stability at room temperature.

  When the photobase generator is used, the 5% mass loss is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, from the viewpoints of storage stability, sensitivity, heat resistance, adhesiveness, and the like.

  In the photosensitive adhesive composition, the amount of (D) the photoinitiator is not particularly limited, but (A) is usually 0.01 to 30 parts by mass with respect to 100 parts by mass of the polyimide having a carboxyl group and / or a hydroxyl group. It is preferable that

  In order to impart storage stability, process adaptability, and antioxidant properties, polymerization inhibitors and oxidation agents such as quinones, polyhydric phenols, phenols, phosphites, and sulfur are previously used as polymerization inhibitors and antioxidants. You may add an inhibitor in the range which does not impair sclerosis | hardenability.

  In the photosensitive adhesive composition, a filler can also be used. Examples of the filler include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, and amorphous. Examples include inorganic fillers such as silica, boron nitride, titania, glass, iron oxide, and ceramics, and organic fillers such as carbon and rubber fillers, and they can be used without particular limitation regardless of the type and shape.

  The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy, etc. to the photosensitive adhesive composition, and the non-metallic inorganic filler is added to the adhesive layer with thermal conductivity, low thermal expansion, low The organic filler is added for the purpose of imparting hygroscopicity, and the organic filler is added for the purpose of imparting toughness to the adhesive layer. These metal fillers, inorganic fillers, or organic fillers can be used singly or in combination of two or more. Among them, a metal filler, an inorganic filler, or an insulating filler is preferable, and an inorganic filler or an insulating filler is preferable in that it can provide conductivity, thermal conductivity, low moisture absorption characteristics, insulating properties, and the like required for an adhesive material for a semiconductor device. Among the fillers, the silica filler is more preferable in that it has good dispersibility with respect to the resin varnish and can impart a high adhesive force when heated.

  The average particle size of the filler is preferably 10 μm or less, the maximum particle size is 30 μm or less, the average particle size is 5 μm or less, and the maximum particle size is more preferably 20 μm or less. If the average particle diameter exceeds 10 μm and the maximum particle diameter exceeds 30 μm, the effect of improving fracture toughness tends to be difficult to obtain. Although there is no restriction | limiting in particular in a lower limit, Usually, both are 0.001 micrometer.

  The filler preferably satisfies both an average particle size of 10 μm or less and a maximum particle size of 30 μm or less. When a filler having a maximum particle size of 30 μm or less but an average particle size exceeding 10 μm is used, it tends to be difficult to obtain high adhesive strength. In addition, when a filler having an average particle size of 10 μm or less but a maximum particle size exceeding 30 μm is used, the particle size distribution tends to be widened and the adhesive strength tends to vary, and the photosensitive adhesive composition is made into a thin film. When processed and used as a film, the surface becomes rough and the adhesive strength tends to decrease.

  Examples of the method for measuring the average particle size and the maximum particle size of the filler include a method of measuring the particle size of about 200 fillers using a scanning electron microscope (SEM). As a measuring method using SEM, for example, a sample obtained by adhering a semiconductor element and a semiconductor mounting support member using an adhesive layer and then heat-curing (preferably at 150 to 200 ° C. for 1 to 10 hours) is used. The method of producing, cutting the center part of this sample, and observing the cross section by SEM etc. is mentioned. At this time, it is preferable that the existence probability of the filler having a particle diameter of 30 μm or less is 80% or more of the total filler.

  In the photosensitive adhesive composition, the content of the filler is determined according to the characteristics or functions to be imparted, but is preferably 1 to 70% by mass, and 2 to 60% by mass with respect to the total of the resin component and the filler. % Is more preferable, and 5-50 mass% is still more preferable. By increasing the amount of filler, a high elastic modulus can be achieved, and dicing performance (cutability by a dicer blade), wire bonding performance (ultrasonic efficiency), and adhesive strength during heating can be effectively improved. If the amount of the filler is increased more than necessary, the thermocompression bonding property tends to be impaired. Therefore, the filler content is preferably within the above range. The optimum filler content is determined in order to balance the required properties. Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

  Various coupling agents can be added to the photosensitive adhesive composition in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective. The usage-amount of the said coupling agent shall be 0.01-20 mass parts with respect to 100 mass parts of polyimide which has (A) carboxyl group and / or a hydroxyl group to use from the surface of the effect, heat resistance, and cost. It is preferable.

  An organic peroxide can also be used as necessary for the thermal curing of the photosensitive adhesive composition. Such an organic peroxide preferably has a one-minute half-life temperature of 120 ° C. or higher, more preferably 150 ° C. or higher. Preparation conditions of the photosensitive adhesive composition, film-forming temperature, curing It is selected in consideration of (bonding) conditions, other process conditions, storage stability, and the like. Although it does not specifically limit as a usable peroxide, For example, 2,5-dimethyl-2,5-di (t-butylperoxy hexane), dicumyl peroxide, etc. are mentioned, Among these, These can be used alone or in admixture of two or more, and the addition amount is preferably 0.1 to 5% by mass.

  An ion scavenger can be further added to the photosensitive adhesive composition in order to adsorb ionic impurities and improve the insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, triazine thiol compound, a compound known as a copper damage preventer for preventing copper from being ionized and dissolved, such as a phenol-based reducing agent, Inorganic compounds such as bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, zuzu-based, and mixed systems thereof. Specific examples include, but are not limited to, inorganic ion scavengers manufactured by Toa Gosei Co., Ltd., trade names, IXE-300 (antimony), IXE-500 (bismuth), IXE-600 (antimony, bismuth mixed). ), IXE-700 (magnesium and aluminum mixed system), IXE-800 (zirconium series), IXE-1100 (calcium series), and the like. These may be used alone or in combination of two or more. The amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyimide having (A) a carboxyl group and / or a hydroxyl group, from the viewpoint of the effect of addition, heat resistance, cost, and the like. .

  In order to improve the storage stability, a radical scavenger such as hindered amine or hindered phenol may be added to the photosensitive adhesive composition. The amount of the radical scavenger used is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of (A) a polyimide having a carboxyl group and / or a hydroxyl group, from the viewpoint of the effect of addition, heat resistance, cost, and the like. .

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Synthesis of polyimide PI-1)
2.28 g of 3,5-diaminobenzoic acid (hereinafter abbreviated as “DABA”), aliphatic ether diamine (“ED400” manufactured by BASF (trade name), (Molecular weight 433) 15.16 g and N-methyl-2-pyrrolidinone (hereinafter abbreviated as “NMP”) were charged. Next, a solution in which 16 g of 4,4′-oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”) was dissolved in NMP was dropped into the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. After completion of dropping, the mixture was further stirred at room temperature for 5 hours. Next, a reflux condenser with a moisture receiver was attached to the flask, xylene was added, the temperature was raised to 180 ° C., and the temperature was maintained for 5 hours. The solution thus obtained was cooled to room temperature and then poured into distilled water for reprecipitation. The obtained precipitate was dried with a vacuum dryer to obtain a polyimide (hereinafter referred to as “polyimide PI-1”).

  When GPC was measured using DMF as a mobile phase, the weight average molecular weight (polystyrene conversion) of polyimide PI-1 was 47000.

  A varnish obtained by mixing polyimide PI-1 with a solvent was applied onto a PET film surface-treated with a release silicone and dried to prepare a polyimide film having a thickness of 40 μm. About the test piece cut out to the size of 35 mm x 10 mm from this film, using the rheometric viscoelasticity analyzer RSA-2, temperature rising rate: 5 degree-C / min, frequency: 1 Hz, measurement temperature: -150 to 300 degreeC The temperature at which tan δ exhibited a maximum value was determined as Tg of polyimide PI-1. In the case where tan δ showed a maximum value at a plurality of temperatures, the temperature showing the maximum maximum value among them was defined as Tg. The Tg of polyimide PI-1 was 50 ° C.

(Synthesis of polyimide PI-2)
2.15 g of 5,5′-methylene-bis (anthranic acid) (hereinafter abbreviated as “MBAA”, molecular weight 286.28) and aliphatic ether in a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device Diamine (BASF “ED400” (trade name), molecular weight 433) 15.59 g and 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane (Shin-Etsu Chemical “LP” -7100 "(trade name), molecular weight 348.4) 2.26 g and NMP were charged. Next, a solution obtained by dissolving 17 g of ODPA in NMP was dropped into the flask while adjusting the temperature of the reaction system so as not to exceed 50 ° C. All subsequent operations were performed in the same manner as the synthesis of polyimide PI-1, and polyimide (hereinafter referred to as “polyimide PI-2”) was obtained.

  When the weight average molecular weight and Tg of polyimide PI-2 were measured under the same conditions as for polyimide PI-1, the weight average molecular weight was 28000 and Tg was 30 ° C.

(Synthesis of polyimide PI-3)
6.83 g of 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter abbreviated as “BAPP”), 4,9-dioxadecane-1,12- in a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device. 3.40 g of diamine (hereinafter abbreviated as “B-12”) and NMP were charged. Subsequently, a solution obtained by dissolving 17.40 g of decamethylene bistrimellitate dianhydride (hereinafter abbreviated as “DBTA”) in NMP was dropped into the flask while adjusting the temperature of the reaction system so as not to exceed 50 ° C. All subsequent operations were performed in the same manner as the synthesis of polyimide PI-1, and polyimide (hereinafter referred to as “polyimide PI-3”) was obtained.

  When the weight average molecular weight and Tg of polyimide PI-3 were measured under the same conditions as for polyimide PI-1, the weight average molecular weight was 89000 and Tg was 73 ° C.

Example 1
Polyimide PI-1, ethoxylated bisphenol A dimethacrylate (“BPE-100” (trade name), manufactured by Shin-Nakamura Chemical Co., Ltd.), and isocyanuric acid EO-modified triacrylate (“M-315” (product) Name), manufactured by Toa Gosei Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“I-819” (trade name), manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator Bisphenol F type liquid epoxy resin as thermosetting resin ("YDF-8170" (trade name), manufactured by Tohto Kasei Co., Ltd.), bisphenol A bis (triethylene glycol glycidyl ether) ether ("BEO-60E" (trade name) ), Shin Nippon Rika Co., Ltd.), and α, α, α′-Tris (4 -Hydroxyphenyl) -1-ethyl-4-isopropylbenzene ("TrisP-PA" (trade name), manufactured by Honshu Chemical Co., Ltd.) uniformly in NMP so as to have the composition (parts by mass) shown in Table 2 By mixing, a varnish for forming an adhesive film was prepared. This varnish was applied onto a PET film surface-treated with a release silicone and dried in an oven at 80 ° C. for 20 minutes and 120 ° C. for 20 minutes to form an adhesive film having a thickness of 40 μm.

(Examples 2 to 10, Comparative Examples 1 to 4)
The raw materials and compositions shown in Tables 1 and 2 were used, respectively. About Examples 2-10 and Comparative Examples 1-4, it carried out similarly to Example 1, and produced the adhesive film.

In addition, the symbol of each component in Table 1 and 2 means the following.
BPE-100: Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A dimethacrylate (bifunctional ester acrylate, SP value: 9.08 (cal / cm ³ ) ^1/2 , molecular weight: about 450)
BPE-200: Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A dimethacrylate (bifunctional ester acrylate, SP value: 9.58 (cal / cm ³ ) ^1/2 , molecular weight: about 600)
BPE-500: manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A dimethacrylate (bifunctional ester acrylate, SP value: 10.58 (cal / cm ³ ) ^1/2 , molecular weight: about 1100)
AH-600: manufactured by Kyoeisha Chemical Co., Ltd., phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (tetrafunctional urethane acrylate, SP value: 12.4 (cal / cm ³ ) ^1/2 , molecular weight: 518)
M-313: manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate (2-3 functional isocyanuric acid acrylate, SP value: about 13 (cal / cm ³ ) ^1/2 , molecular weight: about 350)
A-DCP: Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate (bifunctional ester acrylate, SP value: 9.4 (cal / cm ³ ) ^1/2 , molecular weight: 328)
M-315: manufactured by Toa Gosei Co., Ltd., isocyanuric acid EO-modified triacrylate (trifunctional isocyanuric acid acrylate, SP value: 13.3 (cal / cm ³ ) ^1/2 , molecular weight: 423)
M-215: manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified diacrylate (bifunctional isocyanuric acid acrylate, SP value: 13.7 (cal / cm ³ ) ^1/2 , molecular weight: 369)
UA-21: manufactured by Shin-Nakamura Chemical Co., Ltd. (trifunctional isocyanuric acid acrylate, SP value: 11.9 (cal / cm ³ ) ^1/2 , molecular weight: 1288)
UA-7100: Shin-Nakamura Chemical Co., Ltd., (Trifunctional isocyanuric acid acrylate, SP value: 11.2 (cal / cm ³ ) ^1/2 , molecular weight: 2172)
M-140: manufactured by Toagosei Co., Ltd., N-acryloyloxyethyl hexahydrophthalimide (monofunctional imide acrylate, SP value: 11.6 (cal / cm ³ ) ^1/2 , molecular weight: 251)
DPHA: manufactured by Shin-Nakamura Chemical Co., Ltd., propoxylated dipentaerythritol hexaacrylate (hexafunctional ester acrylate, SP value: 9.11 (cal / cm ³ ) ^1/2 , molecular weight: 570)
YDF-8170: manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin BEO-60E: manufactured by Nippon Nippon Chemical Co., Ltd., bisphenol A bis (triethylene glycol glycidyl ether) ether TrisP-PA: manufactured by Honshu Chemical Co., trisphenol compound (α, α, α′-tris (4-hydroxyphenol) -1-ethyl-4-isopropylbenzene)
R972: Nippon Aerosil Co., Ltd., hydrophobic fumed silica (average particle size: about 16 nm)
I-819: Ciba Specialty Chemicals, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide NMP: Kanto Chemical Co., N-methyl-2-pyrrolidinone

<Evaluation of low temperature adhesiveness>
The adhesive sheets obtained in Examples 1 to 10 and Comparative Examples 1 to 4 are bonded to the back surface (surface opposite to the support table) of the silicon wafer (6 inch diameter, 400 μm thick) placed on the support table. The agent layer was laminated on the silicon wafer side by pressing with a roll (temperature: 100 ° C., linear pressure: 4 kgf / cm, feed rate: 0.5 m / min). Next, the base material (PET film) is peeled off, and a polyimide film having a thickness of 80 μm, a width of 10 mm, and a length of 40 mm (“UPILEX” (trade name) manufactured by Ube Industries, Ltd.) under the same conditions as described above is applied on the adhesive layer. The laminate was pressed with a roll. About the sample prepared in this manner, a 90 ° peel test was performed at room temperature using a rheometer (manufactured by Toyo Seisakusho Co., Ltd., “Strograph ES” (trade name)), and between the adhesive layer and Upilex The peel strength was measured. Based on the measurement results, samples having a peel strength of 2 N / cm or more were evaluated as A, and samples having a peel strength of less than 2 N / cm were evaluated as B. The results are shown in Tables 1 and 2.

<Evaluation of pattern formability>
The adhesive sheet is pressed on a silicon wafer (6 inch diameter, thickness 400 μm) at a temperature of 100 ° C. with a roll with the adhesive layer facing the silicon wafer (linear pressure 4 kgf / cm, feed rate 0.5 m / min) It laminated | stacked by doing.

Next, a negative pattern mask (manufactured by Hitachi Chemical Co., Ltd., “No. G-2” (trade name)) is placed on the substrate (PET film), and a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd., “EXM-1172”). -B-∞ "(trade name)) at 500 mJ / cm ² and left on a hot plate at 80 ° C for about 30 seconds.

  Thereafter, the base material (PET film) was removed, and using a conveyor developing machine (manufactured by Yako Co., Ltd.), a 2.38 mass% solution of tetramethylammonium hydride (TMAH) was used as the developer, the temperature was 28 ° C., and the spray pressure was 0.18 MPa. After spray development under the conditions, the film was washed with pure water at a temperature of 23 ° C. under a spray pressure of 0.02 MPa. After development, whether or not a pattern of line width / space width = 400 μm / 400 μm was formed was visually confirmed, and the case where the pattern was formed was evaluated as A, and the case where the pattern was not formed was evaluated as B. The results are shown in Table 2.

<Measurement of 260 ° C. Peel Strength (Evaluation of Adhesiveness at High Temperature)>
A silicon wafer (6 inch diameter, 400 μm thick) was half cut to a size of 5 mm × 5 mm to a depth of 180 μm. Thereafter, the adhesive sheet was laminated on the half-cut silicon wafer by pressing it with a roll (linear pressure 4 kgf / cm, feed rate 0.5 m / min) on the silicon wafer side at 100 ° C. The obtained sample was exposed at 500 mJ / cm ² with a high-precision parallel exposure machine (“EXM-1172-B-∞” (trade name) manufactured by Oak Manufacturing Co., Ltd.), and about 30 seconds on a hot plate at 80 ° C. I left it alone. Thereafter, the base material (PET film) was removed, and the sample was separated into 5 mm × 5 mm pieces.

  The separated silicon wafer with the adhesive layer was placed on a glass substrate (10 mm × 10 mm × 0.55 mm) with the adhesive layer facing the glass substrate side, and was pressed at 150 ° C. for 10 seconds while being pressurized with 2 kgf. . The test piece thus obtained was heat-cured in an oven at 150 ° C./2 hours. Thereafter, the test piece was heated on a heating plate at 260 ° C. for 10 seconds, and the peel strength of the silicon wafer at 260 ° C. was measured using the peel strength measuring device shown in FIG. The value at this time was defined as 260 ° C. peel strength. The results are shown in Tables 1 and 2.

  In the peel strength measuring device 300 shown in FIG. 13, a handle 32 is provided around the fulcrum 33 at a variable angle at the tip of a rod attached to the push-pull gauge 31. The 260 ° C. peel strength is measured by placing a test piece on which a silicon wafer 34 having a protrusion and a glass substrate 35 are bonded via an adhesive layer 1 on a heating plate 36 at 260 ° C. The peel stress when the handle 32 was moved at 0.5 mm / second in a state where the handle 32 was hooked on the protruding portion 34 was measured by the push-pull gauge 31.

  As is clear from the results shown in Table 2, it was confirmed that the adhesive sheets of the examples were excellent in low-temperature sticking property and pattern formability and sufficiently high in 260 ° C. peel strength as compared with the comparative examples. It was.

It is a schematic cross section showing one embodiment of an adhesive sheet. It is a schematic cross section showing one embodiment of an adhesive sheet. It is a schematic cross section which shows other one Embodiment of an adhesive sheet. It is a schematic cross section which shows other one Embodiment of an adhesive sheet. It is a top view which shows one Embodiment of the semiconductor wafer with an adhesive bond layer. FIG. 6 is an end view taken along line VI-VI in FIG. 5. It is a top view which shows one Embodiment of an adhesive agent pattern. FIG. 8 is an end view taken along line VIII-VIII in FIG. 7. It is a top view which shows one Embodiment of an adhesive agent pattern. FIG. 10 is an end view taken along line XX in FIG. 9. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device. It is a schematic cross section which shows other embodiment of a semiconductor device. It is the schematic which shows a peel strength measuring apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Adhesive layer, 1a, 1b ... Adhesive pattern, 2 ... Cover film, 3 ... Base film (base material), 6 ... Adhesive layer, 7 ... Base film (base material), 8 ... Semiconductor wafer, DESCRIPTION OF SYMBOLS 12, 12a, 12b ... Semiconductor element, 13 ... Supporting member for semiconductor element mounting, 14 ... Wire, 15 ... Sealing material, 16 ... Terminal, 20, 20a, 20b ... Semiconductor wafer with an adhesive layer, 100, 110, 120 , 130 ... Adhesive sheet, 200, 210 ... Semiconductor device, 31 ... Push-pull gauge, 32 ... Handle, 33 ... Support point, 34 ... Silicon wafer, 35 ... Glass substrate, 36 ... Hot plate, 300 ... Peel strength measuring device.

Claims (20)

(A) a polyimide having a carboxyl group and / or a hydroxyl group;
(B) a thermosetting resin;
(C) a radiation polymerizable compound;
(D) a photoinitiator;
Containing
The radiation-polymerizable compound contains a compound having a solubility parameter of 10.0 (cal / cm ³ ) ^½ or more of 20% by mass or more of the whole radiation-polymerizable compound.
Photosensitive adhesive composition. 10.0 (cal / cm ³ ) The compound having a solubility parameter of ^1/2 or more has at least one group selected from the group consisting of an amide group, a urethane group, an isocyanuric group, an imide group, and a hydroxyl group. The photosensitive adhesive composition according to claim 1. The photosensitive adhesive composition according to claim 1 or 2, wherein the compound having a solubility parameter of 10.0 (cal / cm ³ ) ^1/2 or more is a bi- to tetra-functional acrylate and / or methacrylate. The compound having a solubility parameter of 10.0 (cal / cm ³ ) ^1/2 or more is a compound represented by the following general formula (1) or (2). The photosensitive adhesive composition according to Item.

[In formula (1), ^{R 1} represents a divalent organic group having 2 to 30 carbon atoms, an organic group having ^{R 2} and ^{R 3} are independently methacrylate group or acrylate group. ]

[In Formula (2), R ⁴ and R ⁵ represent an organic group having a methacrylate group or an acrylate group, and R ⁶ represents an organic group having a hydroxyl group, a methacrylate group, or an acrylate group. ] The photosensitive adhesive composition according to any one of claims 1 to 4, wherein a molecular weight of the compound having a solubility parameter of 10.0 (cal / cm ³ ) ^1/2 or more is 2000 or less.   The photosensitive adhesive composition as described in any one of Claims 1-5 whose said thermosetting resin is an epoxy resin.   The photosensitive adhesive composition as described in any one of Claims 1-6 in which the said polyimide has a glass transition temperature of 150 degrees C or less and a weight average molecular weight of 5000-150,000.   The photosensitive adhesive composition of Claim 7 whose said polyimide is alkali-soluble.   The photosensitive adhesive composition according to claim 7 or 8, wherein the polyimide is obtained by reacting tetracarboxylic dianhydride and diamine. The photosensitive adhesive composition of Claim 9 in which the said diamine contains the aromatic diamine represented by following Chemical formula (3) or (4).

The photosensitive adhesive composition of Claim 9 or 10 in which the said diamine contains 10-90 mol% of the said diamine with the aliphatic ether diamine represented by following General formula (5).

[Wherein, Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and n ¹ represents an integer of ¹ to 80. ] The photosensitive adhesive composition as described in any one of Claims 9-11 in which the said diamine contains 1-20 mol% of the said diamine with the siloxane diamine represented by following General formula (6).

[Wherein R ⁷ and R ⁸ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent alkyl group having 1 to 5 carbon atoms, phenyl or a phenoxy group, ^{n 2} represents an integer of 1 to 5. ] The photosensitivity as described in any one of Claims 9-12 in which the said tetracarboxylic dianhydride contains the compound represented by following Chemical formula (7) 40 mol% or more of the said tetracarboxylic dianhydride whole. Adhesive composition.

  An adhesive sheet provided with the film-form adhesive bond layer which consists of a photosensitive adhesive composition as described in any one of Claims 1-13.   The adhesive sheet according to claim 14, further comprising a base material, wherein the adhesive layer is provided on one surface of the base material.   The adhesive sheet according to claim 14, further comprising a dicing sheet, wherein the dicing sheet and the adhesive layer are laminated.   It forms by exposing the film-form adhesive layer which consists of a photosensitive adhesive composition as described in any one of Claims 1-13, and developing the said adhesive bond layer after exposure using an alkali developing solution. Adhesive pattern.   A semiconductor wafer with an adhesive layer, comprising: a semiconductor wafer; and an adhesive layer made of the photosensitive adhesive composition according to any one of claims 1 to 13 provided on one surface of the semiconductor wafer.   A support member, a semiconductor element mounted on the support member, and an adhesive layer interposed between the support member and the semiconductor element, wherein the adhesive layer is any one of claims 1 to 13. A semiconductor device, which is formed by the photosensitive adhesive composition described in the item. The adhesive layer which consists of the photosensitive adhesive composition as described in any one of Claims 1-13 is exposed, and the adhesive bond pattern is formed by developing the said adhesive bond layer after exposure using an alkali developing solution. And a process of
Bonding the semiconductor element and the support member on which the semiconductor element is mounted via the adhesive pattern;
A method for manufacturing a semiconductor device comprising:

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